US2008206890A1PendingUtilityA1

Bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(i) complexes, methods of synthesis, and uses therof

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Assignee: WISCONSIN ALUMNI RES FOUNDPriority: Jul 31, 2006Filed: Jul 31, 2007Published: Aug 28, 2008
Est. expiryJul 31, 2026(~0 yrs left)· nominal 20-yr term from priority
Inventors:Judith N. BurstynOmar GreenBhavesh A. Gandhi
H10K 85/371G01N 33/52Y02E10/549C07F 1/005C07F 9/5045H01G 9/2031H01G 9/2059Y02P70/50Y02E10/542
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Claims

Abstract

The present invention provides homoleptic and heteroleptic copper(I) complexes having sterically demanding ligands, such as the bis(2,9-di-tert-butyl-1,10-phenanthroline)copper(I) complex and related complexes, methods of synthesis of these complexes and uses thereof. These copper(I) complexes are useful for various applications including photovoltaic cells, light-emitting electrochemical cells, and analyte sensor systems.

Claims

exact text as granted — not AI-modified
1 . A copper(I) complex having the formula L 1 L 2 CuX wherein X is a negatively charged ion and the ligands L 1  and L 2  are independently selected from 2,9-di-tert-butyl-1,10-phenanthroline, 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline, and 2,9-di-2,4,6-trimethylphenyl-1,10-phenanthroline. 
     
     
         2 . The copper(I) complex of  claim 1  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         3 . A method of synthesizing a copper(I) complex comprising the steps of:
 (a) mixing a ligand L and AgX in a molar ratio of at least 2:1 and solid copper in a polar solvent to result in a (L) 2 CuX complex; and   (b) separating the (L) 2 CuX complex from the reaction of step (a), wherein X is a negatively charged ion.   
     
     
         4 . The method of  claim 3  wherein the polar solvent is selected from acetone, ethanol and tetrahydrofuran. 
     
     
         5 . The method of  claim 3  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         6 . The method of  claim 3  wherein the ligand L is selected from: 1,10-phenanthroline; 2,9-di-neo-pentyl-1,10-phenanthroline; 2,9-di-sec-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9-diphenyl-1,10-phenanthroline; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and 2,9-bis-trifluoromethyl-1,10-phenanthroline. 
     
     
         7 . A method of synthesizing a copper(I) complex comprising the steps of:
 (a) mixing a ligand L 1  with AgX in a molar ratio of about 1:1 and solid copper in a polar solvent to result in a L 1 CuX complex;   (b) isolating the resulting L 1 CuX complex; and   (c) adding about one molar equivalent of ligand L 2  to complex L 1 CuX in a non-polar solvent, resulting in a L 1 L 2 CuX complex; and   (d) separating the L 1 L 2 CuX complex from the reaction of step (c), wherein X is a negatively charged ion.   
     
     
         8 . The method of  claim 7  wherein the ligand L 1  has the same chemical structure as ligand L 2 . 
     
     
         9 . The method of  claim 7  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         10 . The method of  claim 7  wherein the polar solvent of step (a) is selected from acetone, ethanol and tetrahydrofuran. 
     
     
         11 . The method of  claim 7  wherein the non-polar solvent of step (c) is dichloromethane. 
     
     
         12 . The method of  claim 7  wherein ligands L 1  and L 2  are independently selected from: 1,10-phenanthroline; 2,9-di-neo-pentyl-1,10-phenanthroline; 2,9-di-sec-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9-diphenyl-1,10-phenanthroline; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and 2,9-bis-trifluoromethyl-1,10-phenanthroline. 
     
     
         13 . A method of detecting a target molecule in a system having or suspected of having the target molecule, the method comprising the steps of:
 (a) contacting a luminescent copper(I) L 1 L 2 CuX complex with the system having or suspected of having the target molecule;   (b) binding the target molecule to the copper(I) L 1 L 2 CuX complex, wherein the target molecule has a binding constant for Cu(I) that is greater than a Cu(I) binding constant possessed by at least one of the ligands L 1  or L 2 ; and   (c) detecting the presence of the target molecule by measuring a reduction or increase in luminescence of the copper(I) complex.   
     
     
         14 . The method of  claim 13  wherein the target molecule is selected from CO, CH 3 CN, C 2 H 4 , CH 3 NC, C 2 H 2 , NO and O 2 . 
     
     
         15 . The method of  claim 13  wherein the ligands L 1  and L 2  are independently selected from: 1,10-phenanthroline; 2,9-di-neo-pentyl-1,10-phenanthroline; 2,9-di-sec-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9-diphenyl-1,10-phenanthroline; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and 2,9-bis-trifluoromethyl-1,10-phenanthroline. 
     
     
         16 . The method of  claim 13  wherein X is a negatively charged ion. 
     
     
         17 . The method of  claim 16  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         18 . A dye-sensitized photovoltaic cell comprising a light harvesting unit and a sensitizer, wherein the sensitizer is a copper(I) L 1 L 2 CuX complex, wherein L 1  and L 2  are independently selected from: 1,10-phenanthroline; 2,9-di-neo-pentyl-1,10-phenanthroline; 2,9-di-sec-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9-diphenyl-1,10-phenanthroline; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and 2,9-bis-trifluoromethyl-1,10-phenanthroline; and wherein X is a negatively charged ion. 
     
     
         19 . The photovoltaic cell of  claim 18  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         20 . The photovoltaic cell of  claim 18 , wherein the light harvesting unit comprises TiO 2  nanoparticles. 
     
     
         21 . A light-emitting electrochemical cell having an emissive layer, the cell comprising a copper(I) L 1 L 2 CuX complex, wherein L 1  and L 2  are independently selected from: 1,10-phenanthroline; 2,9-di-neo-pentyl-1,10-phenanthroline; 2,9-di-sec-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-1,10-phenanthroline; 2,9-di-tert-butyl-4,7-diphenyl-1,10-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9-diphenyl-1,10-phenanthroline; 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline; and 2,9-bis-trifluoromethyl-1,10-phenanthroline; and wherein X is a negatively charged ion. 
     
     
         22 . The electrochemical cell of  claim 21  wherein the ion X is selected from SO 3 CF 3   − , BF 4   − , SbF 6   − , B(C 6 F 5 ) 4   − , PF 6   −  and ClO 4   − . 
     
     
         23 . A crystalline form of copper(I) complex having unit cell dimensions of about:
 a=11.8246 Å; b=17.8044 Å; and c=27.1111 Å;   a=14.906 Å; b=15.188 Å; and c=16.754 Å;   a=14.7039 Å; b=25.883(3) Å, and c=16.7036(16) Å;   a=14.75449(9) Å, b=15.1383(9) Å, and c=17.9557(11) Å; or   a=12.1995(5) Å, b=13.6275(6) Å, and c=14.4027(6) Å.   
     
     
         24 . The crystalline form of copper (I) complex of  claim 23  wherein the copper(I) complex is [(2,9-di-tert-butyl-1,10-phenanthroline) 2 Cu][B(C 6 F 5 ) 4 ].

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